Reaction products of 4-vinylcyclohexene dioxide



Patented F eb. 13, 1951 REACTION PRODUCTS OF 4-VINYLCYCLO- HEXENE DIOXIDE Gordon Hart Segall and Owen Clement Wentworth Allenby, McMasterville, Quebec, Canada, assignors to Canadian Industries Limited, Montreal, Quebec, Canada, a corporation of Canada No Drawing. Application May 19, 1949, Serial No. 94,256. In Canada February 20, 1948 6 Claims. (01. 260348) This invention relates to new compositions of matter. More particularly it relates to new hydroxy esters. Still more particularly, it relates to monohydroxy monoester oxides and dihydroxy diesters obtained from 4-viny1cyc1ohexene dioxide and carboxylic acids.

I gi-vinylcyclohexene dioxide, a compound having the structure CHCH2 may be prepared by reacting 4-vinylcyclohexene with hypochlorous acid whereby 4-vinylcyclohexene dichlorohydrins are obtained, and by dehydrohalogenating the dichlorohydrins to obtain the dioxide. Because of the presence of two epoxide rings in its molecule, it would be expected that 4-viny1cyclohexene dioxide Would react readily with carboxylic acids like other known organic epoxy compounds and thus give monohydroxy mono-ester oxides and dihydroxy diesters according to the following equations:

CH-(FHa on RCO o 2R-COOH CH-OH2 HO sir-cm..-

and/or (5H 500R and/or HO- oH-cm RCO and/or RG00 ctr-0H,

H RCO Nowhere in the literature, however, is reference made of the above esters. Furthermore, in the absence of catalysts, or in the presence of in-v efii'cient catalysts such as the usual esterifical tion catalysts or primary, secondary, or tertiary amines, or in the presence of insuflicient amounts of efl'icient catalysts, the reaction between'carboxylic acidsand 4-vinylcyc1ohexene dioxide does not result in the formation of monohydroxy intramolecular reaction between the hydroxyl groups and the epoxide groups to form internal ethers, probably tetrahydropyran; rings- An ;ex-.

ample of such intramolecular reaction is given by the following equation:

RCOO

HO CH-CH:

It has been found that when catalysts such as trimethylbenzylammonium hydroxide, tetra, methylammonium hydroxide, guanidine, potassium or lithium hydroxides are used in concentrations of from one to eight per cent of the weight of the reactants, monohydroxy monoester oxides or dihydroxy diesters may be obtained readily depending on the molar amount of carboxylic acids which are reacted with i-vinylcyclohexene dioxide.

It is therefore an object of this invention to provide hydroxy esters from 4-vinylcyclohexene dioxide and carboxylic acids. 'Another object is to provide monohydroxy monoester oxides and dihydroxy diesters from 4-vinylcyclohexene dioxide and carboxylic acids. A further object is the provision of a process for the preparation of these esters. Other objects will appear hereinafter.

These and other objects are accomplished by the invention hereinafter described which broadly comprises reacting 4-vinylcyclohexene dioxide with carboxylic acids of the general formula R-COOI-I, wherein R is an organic radical, in the presence of a catalyst selected from the group consisting of strong inorganic and organic bases.

Mor particularly, this invention may be described as follows. One or two mols of 'a carboxylic acid are mixed with a catalyst selected from the group consisting of strong inorganic and organic bases, such as trimethylbenzylammonium hydroxide, in the proportion of from 1 to 8% by weight, of the reaction mixture, and

then heated to a temperature of about 100- 150 C. One mol of 4-vinylcyclohexene dioxide is thereafter quickly added to the heated'inixture and the esterification allowed to proceed at 100-150 C. until completion.

The following examples are illustrative of the more detailed practice of this invention and are not to be construed as restricting or limiting the scope of the invention in any way.

Example! TQ 12g. (02 mol) 'acetic acid dissolved in 46g. methyl isobutyl ketone, there was added 3 g. triethy n ammo um a e t a d the mi ur washeated to 110 C. 31 g. (0.2 mol) ll-vinyl cyel hexen x e, al i 90%. was t added instantaneously theretoand the tempera-. ture readjusted to 110 C. where it was main: tained. The following table shows the rateof 4 esterification through the residual acid and oxide equivalent values:

- Acid equiv- Oxide equiv- Tlme alent alent 'to. The mixture was then heated to 110 C. at

which temperature 31 g. (0.2 mol) 4-viny1cyc1o hexene dioxide, analyzing was added and the esterification allowed to proceed. The following results were obtained:

- Acid equiv- Oxide equiv- Tlme en alent The product was a solution of i viny l'cycloe hexene monohydroxy monocrotonate oxides. The neutral solution was unstable with respect to oxide content.

Example III. To 23 g. (0.2 mol) sorbic' acid and l g. trimethylbenzylammonium hydroxide heated to 130 -C.-, therewas added 55 g. aromatic hydro:

carbon solvent and the temperature was-brought dioxide, analyzing- 90%, was then added andthe esterification allowed to proceed at ,-.-"witii=- the following results:

- cid. I O e Tune equivalent equivalent.

The product was a solution 4-vinylcyclohexene monohydroxymonosorbate oxides.

Example IV 54 g. (0.2 mol) stearic acid was mixed with 0.1" g. trimethylbenzylammonium hydroxide as a 40% aqueous solution and the mixture heated to C. 31 g. (0.2 mol) 4-vinylcyclohexenegdi oxide, analyzing 90%, was then added thereto and the temperature readjusted and kept at 120 C. The following rate of esterification was observed:

- Acid equiva- Oxide equiva- Tlme lent lent The product, awax, was 4-vinylcyclohexene monohydroxy monostearate oxides in which some intramolecular isomerization had presumably occurred.

Example V The procedure of Example IV was repeated, but at a temperature of 150 C. instead of 120 C.

with the following results:

. Acid equiva- Oxide equiva- Tlme lent lent The product had a chemical nature similar to that of Example IV product.

Example VI To a mixture of 5 g. (0.2 mol) stearic acid and 1 g. trimethylbenzylammonium hydroxide (40% aqueous solution) heated to 110 0., there was added 31 g. (0.2 mol) l-vinylcyclohexene dioxide, analyzing 90%, and after the temperature was readjusted to 110 C., the esterification was allowed to proceed. The following values of residual acid and oxide equivalents at different time intervals illustrate the rate of the reaction:

- Acid Oxide Tune equivalent equivalent The product was e-vinylcyclohexene monohydroxy monostearate oxides. It was a neutral low melting wax containing one equivalent of active hydrogen and one oxide ring per formula weight I Example VII The esterification of Example VI was repeated at 120 C. with the following results:

. Acid Oxide Time equivalent equivalent The product, a wax, was a mixture of unstable 4-vinylcyclohexene monohydroxy monostearate oxides and, presumably, isomerized and polymerized forms thereof.

Example VIII 54 g. (0.2 mol) stearic acid was mixed with 5 g. tetramethylammonium stearate and the mixture was heated to 120 C. 31 g. (0.2 mol) 4+ vinylcyclohexenedioxide, analyzing 90%, was then added to the heated mixture and the esterification conducted at 120 C. After 10 minutes of heating, there was 0.011 residual acid equivalent -and'0.218 residual oxide equivalent.

The waxy product was 4-vinylcyclohexene monohydroxy monostearate oxides.

Example IX 54-. g. (0.2 mol) stearic acid was mixed with 0.1 mol quinoline and the mixture heated to 200 C. 29.5 g. (0.19 mol) 4-Vinylcyc1ohexene dioxide, analyzing was then added thereto and the temperature maintained at 200-220 C. The following rate of esterification was observed:

- Acid equiv- Oxide equiv- Tlme alent alent The molecular weight of the product was 400, active hydrogen found 1.03, carbonyl content negligible. This material corresponded to a bicyclic compound, produced by intramolecular rearrangement of the 4-vinylcyclohexene monohydroxy monostearate oxides, said compound having a molecular weight of 410, one active hydrogen and zero oxide value.

Example X Example XI To a mixture of 57 g. (0.2 mol) linseed oil acids and 1 g. trimethylb'enzylammonium hydroxide (40% aqueous solution) heated to C., there was added 31 g. (0.2 mol) l-vinylcyclohexene dioxide, analyzing 90%, and the reaction was allowed to proceed at 110 C. The following results were obtained:

Acid equiv- Oxide equiv- Tune alent alcnt The oily product was l-vinylcyclohexene monohydroxy linseed oil acids monoester oxides.

Example XII An esterification similar to that of Example XI was carried on at C. with the following results:

. Acid equiv- Oxide equiv- Tlme alent alent A product similar to that of Example XI was obtained. I

' Example XIII.

A mixture of 57 g. (0.2 mol) linseed oil acids, 1 g. trimethylbenzylammonium hydroxide (40% aqueoussolution) and 89 g. aromatic hydrocarbon solvent was heated to. 120 C. at whichtemperature 31 g. (0. 2 mol) .4-vinylcyclohexene dioxide, analyzing 90%, was added and the esterification allowed toproceedr The followingmesults were. obtained:

, Acid Oxide Tune equivalent equivalent 0. 200 i O. 400 13' 0. 120 0. 362 30. O. 078 0. 305 45 0. 046 0. 264

f" The mixture was afterwards heated to'145 C. for some time and. an analysis for residual acid and oxide equivalent carried th'ereon'with'th'e following results:

Acid Oxide equivalent equivalent The'product was a solution of e-vinylcyclohe'xene monohydroxy linseed oil acids mono'ester oxides? Example XIV Anesterifi'eation similar 'to'that. of Example XIII was made at 150 C. using 118 'g. aromatic hydrocarbon solvent. The rate of the reaction was asfollows:

Acid equiva- Oxide equiva- Tlme lent lent 0 0.200 (I. 400. 0.072 0. 278 O. (141' I 0. 249 30 0.011 0. 209

There was obtained a productsimilar to that of ExampleXIII.

Example XV To 57 g. (0.2 mol) linseed oil acids and 1.5 g. tetramethylammonium hydroxide heated to 120 0., there was. added 31 g. (0.2 mol) l-vinylcyclohexene dioxide, analyzing 90%, and the esterication was-allowed to proceed at 120 C.- with the following. results:

- Acid equivm Oxide equiva- Tlme lent lent The product'obtained was the same as that of Example XI.

Example XVI The procedureof Example XV was applied to 5'Lgu (0.2 mol) linseed oil acids, 1 g. tetramethylammonium hydroxide and 31 g. (1O.2 n 1ol)..4-

8:? vinylcyclohexene dioxide, analyzing 90%; butin the. presence of 89 g. aromatic hydrocarbon sol. vent and at 140 C;- The following results were obtained.

Acid Oxide Tune equivalent equivalent The oily product was a solution of 4-vinylcyclohexenei monohydroxylinseed oil acids monoester oxides.

Example XVII 5'? g. (0.2 mol) linseed oil acids were mixed 61 g., (0.2 mol) linseed oil acids were mixed with 1 g. potassium hydroxide and the mixture heated to 120 C. 31 g. (0.2 mol) 4-vinylcy'clo-' hexene dioxide, analyzing.90%, was then added thereto and the reaction continued at 120 C. with the following results:

Acid equiv- Oxide equiv- Tlme alent alent The chemical nature of the product was the same as that of Example XVII product.

Example XIX The procedure of Example XVIII was applied to 62.7 g.5(0'.2 mol) linseed'oil acids, 0.5 g. lithium hydroxide and 31 g. (0.2 mol) 4-vinylcyclohexene dioxide, analyzing The following results were obtained:

Acid equiv- Oxide equiv- Tlme alent alent The product was thatof Example XVIII.

Example XX I in62.5 g. methyl isobutyllretone, .the'rewas added 6.5 .g. .trimethyl benzylammonium benzoate and the mixture was heated to C.. 31 g. (0.2 mol) {l-vin ylcyclohexene dioxide, analyzing .90.%,.wa$

then added to theheated mixture and thewesteri To a solution of 24.5 g. .-(0.'2 mol .benzoic acid "fication allowed to proceed at 100C. with the following results: 1

Acid equiv- Oxide equiv- Tlme Y alent alent The product was a methyl isobutyl ketone s0- lution of 4-vinylcyclohexene monohydroxy monobenzoate oxides.

Example XXI 24 g. (0.4 mol) acetic acid was dissolved in 64 g. methyl isobutyl ketone and 9 g. trimethylbenzylammonium acetate was added. The mixture was then heated to 110 C. at which temperature 31 g. (0.2 mol) 4-vinylcyclohexene dioxide, analyzing 90%, was quickly added and the di-esterification allowed to proceed. The following rate of esterification was observed:

- Acid equiv- Oxide equiv- Txme alent alent The product was a solution of 4-vinylcyclohexene dihydroxy diacetates. It was dark in colour but stable,

Example XXII To 34 g. (0.4 mol) crotonic acid dissolved in 75 g. cyclohexanone, there was added 10 g. trimethylbenzylammonium crotonate and the mixture was heated to 110 C. 31 g. (0.2 mol) 4-vinylcyclohexene dioxide, analyzing 90%, was then added and the esterification carried on at 110 C. with the following results:

1 Acid equiva- Oxide equiva- Tune lent lent The product was a solution of l-vinylcyclohexene dihydroxy dicrotonates.

Emample XXIII:

54 g. (0.2 mol) stearic acid was heated,- to "1110?: C; with "1 g. 'trimethylbenzylammonium *hydroXi'de as a 40% aqueous solution and 155 g.

(0.1 mol) 4-vinylcyc1ohexene dioxide, analyzing 90%, was then added thereto. The temperature was thereafter readjusted to 110 C. and the diesterification allowed to proceed with the following results:

Acid equiva- Oxide equiva- Tlme lent lent The product was a wax consisting of lYi ll-- .cyclohexene dihydroxy distear'at'es.

'310 .Ezcar'nzole XXIV To .108 g. (0.4 mol) .stearic. acid heated to 120 C. with 2 g. trimethylbenzylammonium hydroxide (40% aqueous solution), there was added 31 g. (0.2 mol) 4-vinylcyclohexene dioxide, analyzing and the reaction continued at C. The following di-esterification rate was obtained:

. Acid Oxide T equivalent equivalent 5 I The product, l-vinylcyclohexene dihydroxy distearates, was a stable, neutral, low melting wax. Molecular weight; found 6'70, calculated 680. Active hydrogen: found 2.06, calculated 2.00 equivalents per 680 g.

Example XXV A mixture of 57.5 g. (0.2 mol) stearic acid and 2.7 g. potassium hydroxide (50% aqueous solution) was prepared and heated to-120 C. 15.5 g. (0.1 mol)' l-vinylcyclohexene dioxide, analyzing 90%, was then added thereto and the di-esterification allowed to proceed at 120 C. with the following results i Acid equiv- Oxide equivalent alent 0'? 0. 200 0.200 it 0.087 0. 087 30' 0. 059; 0. 059 60' r 0. 036' 0. 010 90' 0.016 0. 010

The product was that of Example XXIII.

Example XXVI Theprocedure .ofExample XXV was applied to 63.3 g. (0.2 mol) stearic acid, 0.5 g. lithium A product similar to that of Example XXIII was obtained.

Example XXVII A reaction similar to that of Example XXVI was conducted at C. with the following results:

Acid equiv- Oxide equiv- Tlme alent alent The waxy product was impure 4-vinylcyclohexene. dihydroxy distearates.

Example XX V1. I "To a mixture of 56 g. 0.2 ncl)" oleic acid and 1.0 g. trimethylbenzylam nonium hydroxide he t C.. th re Was a d 15- I mol) i-vinylcyclohexene dioxide, analyzing 90%,

'- and the reaction was allowed to proceed at 120 C; The following results were obtained:

Acid Oxide Time equivalent equivalent The viscous liquid product was i-vinylcycle hexene dihydroxy dioleates.

Ewa zz e X IX 49 g. (0.4 mol) benzoic acid was dissolved in 90 g. methyl isobutyl ketone and g. trimethylbenzylammoniumbenzoate was added. thereto. The mixture was then heated to 100 C.v at which temperature 31 g. (0.2 mol) 4-vinylcyclohexene l dioxide, analyzing, 90%, was added and the reaction continued, at 100 C. The following results were obtained:

, Acid Oxide Elma equivalent equivalent he. product was a meth lx sebiityl keto esolution of impure e-vinylcyclohexene dihydroxy dibenzoates.

The monohydroxy monoester oxides 7 may be used immediately without. purification in further reaction involving the oxide and hydroxylgroups.

Continued heating of these compounds,.as. il-

lustrated in Examples VII; .XI', XII and XV results in oxide lost presumably with the formation of a mixture of the unstable monohydroxy monoester oxides and their polymerized forms. .In the case of the monohydroxy monostearate oxides the product resulting from oxideloss has been found to have an increased molecular weight and has been observed; to have reduced solubility in acetone;

and ether. Themelt also is-more viscous and cryst llizes less readily thant e monohydr xy monoester oxides.

Esterification at elevated temperatures (Example V) or with insuflicient amount of catalyst "-i xamrle V) or ith an inef ici nt ca al st hydroxide monoester oxides derived from some lower acids required both an inert solvent and isomerized and l i a al ncen ration iiabcut a% .----m avoid the side reactions which resultiin oxide loss- Unlike the. simi ar. products. de i d m long chain acids, such monohydroxy monoester oxide solutions are not stable.

Although temperaturesof from to 150 C. are suitable for effecting the esterification, a range of -120 C. is preferred inasmuch as lower values require further heating of the reactants and higher values require greater concentrations of catalysts.

Y Other catalysts than those 'menti'oned in 'the previous examples are suitable for the operation of this invention. Examples of such catalysts are the strong inorganic bases other than potass m h droxid and t e str ng organ c, ba s such as amidines, N-alkyl guanidines. and quater y mmen m c mpounds. th r man etram thy mo ium hydroxide and. trim thiilbenzylammonium hydroxide.

The monohydroxy monoester oxides and. dihydroxy diesters of this invention may befu ther reacted with monocarboxylic acids. to, give tri and tetra esters. When reacted with dicarboxylic acids, they yield linear or cross-linked polyesters containing ester side-cha ns which are structurally related to the modified alkyd resins and the similar resins based on pentaerythritol.

The monohydroxy monoester oxides ;,of the invention may also be reacted with acid anhydrides to yield polyesters. In the case of monoesters derived from unsaturated acids, the reaction with anhydridesmay lead to drying resins? The esters of this invention are also useful as plasticizers and lubricating agents.

Having thus described our invention what we c aim is:

1. A process for preparing monohydroxy monoester oxides which comprises reacting} one mol of l-vinylcyclohexene dioxide with one mol of long chain fatty acid at a temperature of from 100 C. to 150 C. and in the presence of at least 1% by weight of the reaction mixture of a catalyst selected from the group consisting of potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide.

2. A process for preparing monohydroxy monoester oxides which comprises reacting one mol of 4-vinylcyclohexene dioxide with one mol of long chain fatty acid at a temperature of from 110 C. to C. and in the presence of at. least 1% by Weight of. the reaction mixture of a catalyst selected from the group-6.0 sisting of potassium hydrgxide, lithium hydroxide, tetramethylammonium hydroxide and -trimethylbenzylammonium hydroxide.

3. A process for preparing monohydroxy monoester oxides which comprises reacting one mol of 4-vinylcyclohexene dioxide with one mol of long chain fatty acid at a temperaturel'of from 110 C. to 120 C. and in the presence of atleast 1% by weight of the reaction mixture of trimethylbenzylammonium hydroxide...

4. A process for preparing monohydroxy monoester oxides which comprises reacting one mol of e-vinylcyclohexene dioxide with one mol of stearic acid at a, temperature off-rom 110 C. to 120 C. and in the presence of at least 1% by weight of the reaction mixture-of trimethylbenzylammonium hydroxide.

5. A process for preparing monohydroxy -monoester oxidesv which. comprises reacting: 0ne

mol of 4-vinylcyclohexene dioxide withyonegmol 14 of-oleic acid at a temperature of from 110 C. REFERENCES CITED to 120 C. and in the presence of at least 1% by weight of the reaction mixture of trimethy1 The following references are of record in the benzylammonium hydroxide. me of this patent:

6. A process for preparing monohydroxy 5 UNITED STATES PATENTS monoester oxides which comprises reacting one mol of 4-viny1cyclohexene dioxide with one mol Number m Date of linseed oil acid at a temperature of from .5 O hner Aug-10,1937 110 0. to 120 c. and in the presence of at 2.131,142 Orthner 4 Sep '7. 1 8 least 1% by weight of the reaction mixture of u trimethylbenzylammonium hydroxide. OTHER REFERENCES GORDON HART SEGALL, Goldsmith, pp. 274 and 275, Chemical Reviews, OWEN CLEMENT vol. 33, No. 3, December 1942.

WENTWORTH ALLENBY. 

1. A PROCESS FOR PREPARING MONOHYDROXY MONOESTER OXIDES WHICH COMPRISES REACTING ONE MOL OF 4-VINYLCYCLOHEXENE DIOXIDE WITH ONE MOL OF LONG CHAIN FATTY ACID AT A TEMPERATURE OF FROM 100* C. TO 150* C. AND IN THE PRESENCE OF AT LEAST 1% BY WEIGHT OF THE REACTION MIXTURE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF POTASSIUM HYDROXIDE, LITHIUM HYDROXIDE, TETRAMETHYLAMMONIUM HYDROXIDE AND TRIMETHYLBENZYLAMMONIUM HYDROXIDE. 